CHAPTER

Electronic Structure of
Atom
From Indivisible to Quantum
Mechanical Model of the Atom

1
 Classical Model

Democritus
Dalton
Thomson
Rutherford

2
Democritus

Circa 400 BC
Greek philosopher
Suggested that all matter is
composed of tiny, indivisible
particles, called atoms

3
Dalton’s Atomic Theory (1808)
1. All matter is made of tiny indivisible particles called
atoms.
2. Atoms of the same element are identical. The
atoms of any one element are different from those
of any other element.
3. Atoms of different elements can combine with one
another in simple whole number ratios to form
compounds.
4. Chemical reactions occur when atoms are
separated, joined, or rearranged; however, atoms
of one element are not changed into atoms of
another by a chemical reaction.

4
J.J. Thomson (1897)
Determined the charge to mass
ratio for electrons
Applied electric and magnetic
fields to cathode rays (waves)
“Plum pudding” model of the
atom

5
Rutherford’s Gold Foil Experiment
(1910)

Alpha particles (positively charged

helium ions) from a radioactive source
was directed toward a very thin gold
foil.
A fluorescent screen was placed behind
the Au foil to detect the scattering of
alpha (α ) particles.

6
7
Rutherford’s Gold Foil Experiment
(Observations)

Most of the α -particles passed

through the foil.
Many of the α -particles deflected
at various angles.
Surprisingly, a few particles were
deflected back from the Au foil.

8
Rutherford’s Gold Foil
Experiment (Conclusions)

Rutherford concluded that most of the

mass of an atom is concentrated in a
core, called the atomic nucleus.
The nucleus is positively charged.
Most of the volume of the atom is
empty space.

9
Shortfalls of Rutherford’s
Model
Did not explain where the atom’s
negatively charged electrons are
located in the space surrounding its
positively charged nucleus.
We know oppositely charged particles
attract each other
What prevents the negative electrons
from being drawn into the positive
nucleus?

10
Bohr Model (1913)

Niels Bohr (1885-1962), Danish

scientist working with Rutherford
Proposed that electrons must have
enough energy to keep them in
constant motion around the
nucleus
Analogous to the motion of the
planets orbiting the sun
11
Planetary Model

The planets are attracted to the

sun by gravitational force, they
move with enough energy to
remain in stable orbits around the
sun.
Electrons have energy of motion
that enables them to overcome the
attraction for the positive nucleus

12
Think about satellites….

We launch a satellite into space

with enough energy to orbit the
earth
The amount of energy it is given,
determines how high it will orbit
We use energy from a rocket to
boost our satellite.

13
Electronic Structure of
Atom

Waves-particle duality
Photoelectric effect
Planck’s constant
Bohr model
de Broglie equation

14
Radiant Energy
Radiation ≡ the emission of energy in various forms
A.K.A. Electromagnetic Radiation
Radiant Energy travels in the form of waves that have both
electrical and magnetic impulses
Electromagnetic Radiation ≡ radiation that consists
of wave-like electric and magnetic fields in space,
including light, microwaves, radio signals, and x-
rays
Electromagnetic waves can travel through empty
space, at the speed of light (c=3.00x108m/s) or
about 300million m/s!!!

15
Waves
 Waves transfer energy from one place to
another
• Think about the damage done by waves during
strong hurricanes.
• Think about placing a tennis ball in your bath tub, if
you create waves at one it, that energy is
transferred to the ball at the other = bobbing
 Electromagnetic waves have the same
characteristics as other waves
 

16
 Wave Characteristics

Wavelength, λ (lambda) ≡ distance between

successive points

2
m

10
m

17
Wave Characteristics

Frequency, ν (nu) ≡ the number of

complete wave cycles to pass a given point
per unit of time; Cycles per second

t=0 t=5
t=0 t=5

18
Units for Frequency

1 cycle/s
s-1
hertz, Hz
Because all electromagnetic waves travel
at the speed of light, wavelength is
determined by frequency
Low frequency = long wavelengths
High frequency = short wavelengths

19
Waves
Amplitude ≡ maximum height of a wave

20
Waves
Node ≡ points of zero amplitude

21
Electromagnetic
Spectrum
Radio & TV, microwaves, UV,
infrared, visible light = all are
examples of electromagnetic
radiation (and radiant energy)
Electromagnetic spectrum: entire
range of electromagnetic radiation

22
Electromagnetic Spectrum
Frequenc
1024 1020 1018 1016 1014 1012 1010 108 106 y Hz

Gamma Xrays UV Microwaves FM AM

IR

10-16 10-9 10-8 10-6 10-3 100 102Wavelength m

Visible Light

23
Notes
Higher-frequency electromagnetic waves
have higher energy than lower-frequency
electromagnetic waves
All forms of electromagnetic energy
interact with matter, and the ability of these
different waves to penetrate matter is a
measure of the energy of the waves

24
What is your favorite radio
station?

Radio stations are identified by

their frequency in MHz.
We know all electromagnetic
radiation(which includes radio
waves) travel at the speed of
light.
What is the wavelength of your
favorite station?
25
Velocity of a Wave
Velocity of a wave (m/s) = wavelength (m) x
frequency (1/s)
c=λ ν
c= speed of light = 3.00x108 m/s
Eg: My favorite radio station is 105.9
Jamming Oldies!!! What is the
wavelength of this FM station?

26
Wavelength of FM
Answer:

c =λ ν
c= speed of light = 3.00x108 m/s
ν = 105.9MHz or 1.059x108Hz
λ = c/ν = 3.00x108 m/s = 2.83m
1.059x1081/s

27
What does the electromagnetic
spectrum have to do with
electrons?

It’s all related to energy - energy

of motion (of electrons) and
energy of light

28
Light
States of Electrons
When current is passed through a gas at a
low pressure, the potential energy (energy
due to position) of some of the gas atoms
increases.
Ground State: the lowest energy state of an
atom
Excited State: a state in which the atom has
a higher potential energy than it had in its
ground state

30
Excited State
Absorbance and Emission
Absorbance and Emission
Quantization
Neon Signs
When an excited atom returns to
its ground state it gives off the
energy it gained in the form of
electromagnetic radiation!
The glow of neon signs, is an
example of this process

35
White Light
White light is composed of all of the
colors of the spectrum = ROY G BIV
When white light is passed through a
prism, the light is separated into a
spectrum, of all the colors
What are rainbows?

36
Line-emission Spectrum
When an electric current is
passed through a vacuum tube
containing H2 gas at low pressure,
and emission of a pinkish glow is
observed.
What do you think happens when
that pink glow is passed through
a prism?

37
Hydrogen’s Emission Spectrum

The pink light consisted of just a few specific

frequencies, not the whole range of colors as with
white light
Scientists had expected to see a continuous
range of frequencies of electromagnetic radiation,
because the hydrogen atoms were excited by
whatever amount of energy was added to them.
Lead to a new theory of the atom

38
Bohr’s Model of Hydrogen
Atom
Hydrogen did not produce a continuous
spectrum
New model was needed:
 Electrons can circle the nucleus only in
allowed paths or orbits
 When an e- is in one of these orbits, the
atom has a fixed, definite energy
 e- and hydrogen atom are in its lowest
energy state when it is in the orbit closest
to the nucleus

39
Bohr Model Continued…
 Orbits are separated by empty space,
where e- cannot exist
 Energy of e- increases as it moves to
orbits farther and farther from the
nucleus

(Similar to a person climbing a ladder)

40
Bohr Model and Hydrogen
Spectrum
While in orbit, e- can neither gain or lose energy
But, e- can gain energy equal to the difference
between higher and lower orbitals, and therefore
move to the higher orbital (Absorption)
When e- falls from higher state to lower state, energy
is emitted (Emission)

Bohr’s Calculations
Based on the wavelengths of hydrogen’s line-
emission spectrum, Bohr calculated the
energies that an e- would have in the allowed
energy levels for the hydrogen atom
41
Photoelectric Effect
An observed phenomenon, early 1900s
When light was shone on a metal, electrons
were emitted from that metal
Light was known to be a form of energy,
capable of knocking loose an electron from a
metal
Therefore, light of any frequency could supply
enough energy to eject an electron.

42
Photoelectric Effect : Situation
Light strikes the surface of a metal
(cathode), and e- are ejected. These
ejected e- move from the cathode to the
anode, and current flows in the cell. A
minimum frequency of light is used. If
the frequency is above the minimum and
the intensity of the light is increased,
more e- are ejected.

43
Photoelectric Effect
cont.
Observed: For a given metal, no
electrons were emitted if the light’s
frequency was below a certain
minimum, no matter how long the
light was shone
Why does the light have to be
of a minimum frequency?

44
Explanation….
Max Planck studied the emission of light
by hot objects
Proposed: objects emit energy in small,
specific amounts = quanta
(Differs from wave theory which would say objects emit
electromagnetic radiation continuously)

Quantum: is the minimum quantity of energy

that can be lost or gained by an atom.

45
Planck’s Equation
E radiation = Planck’s constant x
frequency of radiation
E = hν
h = Planck’s constant
= 6.626 x 10-34 J s
•

When an object emits radiation, there

must be a minimum quantity of energy
that can be emitted at any given time.

46
Einstein Expands Planck’s
Theory
Theorized that electromagnetic
radiation had a dual wave-particle
nature!
Behaves like waves and particles
Think of light as particles that each
carry one quantum of energy =
Photons
photons
Photons: a particle of electromagnetic
radiation having zero mass and carrying a
quantum of energy
Ephoton = hν
47
Back to Photoelectric
Effect

Einstein concluded:
 Electromagnetic radiation is
absorbed by matter only in whole
numbers of photons
 In order for an e- to be ejected, the
e- must be struck by a single
photon with minimum frequency

48
Example of Planck’s Equation
CD players use lasers that emit red light with a λ of
685 nm. Calculate the energy of one photon.
 Different metals require different minimum
frequencies to exhibit photoelectric effect

Answer

Ephoton = hν
h = Planck’s constant = 6.626 x 10-34 J•s
c =λ ν
c = speed of light = 3.00x108 m/s
ν = (3.00x108 m/s)/(6.85x10-7 m)
ν = 4.37x1014 1/s
Ephoton = (6.626 x 10-34 J•s)(4.37x1014 1/s)
Ephoton = 2.90 x 10-19 J 49
Wave Nature of Electrons
We know electrons behave as particles
In 1925, Louis de Broglie suggested that
electrons might also display wave
properties
de Broglie’s Equation
A free e- of mass (m) moving with a
velocity (v) should have an associated
wavelength: λ = h/mv
Linked particle properties (m and v) with
a wave property (λ )
50
Example of de Broglie’s Equation

Calculate the wavelength associated with

an e- of mass 9.109x10-28 g traveling at
40.0% the speed of light. [Hint.: 1 J = 1 kg
m2/s2]
Answer:
v=(3.00x108m/s)(.40)=1.2x108m/s

λ = h/mv
λ = (6.626 x 10 -34
J•s) =6.06x10-12 m
(9.11x10-31 kg)(1.2x108m/s)
Remember 1J = 1(kg)(m)2/s2

51
Wave-Particle Duality
de Broglie’s experiments
suggested that e- has wave-like
properties.
Thomson’s experiments
suggested that e- has particle-like
properties
 measured charge-to-mass ratio

52
Quantum mechanical
model
SchrÖdinger
Heisenberg
Pauli
Hund

53
Where are the e- in the atom?
e- have a dual wave-particle nature
If e- act like waves and particles at the
same time, where are they in the atom?
First consider a theory by German
theoretical physicist, Werner Heisenberg.

54
Heisenberg’s Idea
e- are detected by their interactions with
photons
Photons have about the same energy as e-
Any attempt to locate a specific e- with a
photon knocks the e- off its course
ALWAYS a basic uncertainty in trying to locate
an e-

Heisenberg’s Uncertainty Principle

Impossible to determine both the
position and the momentum of an e- in
an atom simultaneously with great
certainty. 55
SchrÖdinger’s Wave
Equation
An equation that treated electrons in atoms
as waves
Only waves of specific energies, and
therefore frequencies, provided solutions to
the equation
SchrÖdinger’s Wave
Quantization of e- energies was a natural
Equation
outcome

Solutions are known as wave functions

Wave functions give ONLY the probability of
finding and e- at a given place around the
nucleus
e- not in neat orbits, but exist in regions
called orbitals 56
SchrÖdinger’s Wave
Equation
Here is the equation
Don’t memorize this or write it down
It is a differential equation, and we need
calculus to solve it

-h = (ә2 Ψ )+ (ә2Ψ )+( ә2Ψ ) +Vψ =Eψ

8(π)2m (әx2) (әy2) (әz2 )

Scary???

57
Definitions
Probability ≡ likelihood
Orbital ≡ wave function; region in space
where the probability of finding an electron is
high
SchrÖdinger’s Wave Equation states that
orbitals have quantized energies
But there are other characteristics to
describe orbitals besides energy

58
 Quantum Numbers
Definition: specify the properties of
atomic orbitals and the properties of
electrons in orbitals
There are four quantum numbers
The first three are results from
SchrÖdinger’s Wave Equation

59
Quantum Numbers (1)
Principal Quantum Number, n

60
Quantum Numbers
Principal Quantum Number, n
 Values of n = 1,2,3,… ∞
 Positive integers only!
 Indicates the main energy level
occupied by the electron

61
Quantum Numbers
Principal Quantum Number, n
 Values of n = 1,2,3,… ∞
 Describes the energy level, orbital
size

62
Quantum Numbers
Principal Quantum Number, n
 Values of n = 1,2,3,… ∞
 Describes the energy level, orbital
size
 As n increases, orbital size
increases.

63
 Principle Quantum
Number
n=6
n=5
n=4
n=3

Energy n=2

n=1

64
Principal Quantum
Number
Principle Quantum
Number
More than one e- can have the same
n value
These e- are said to be in the same e-
shell
The total number of orbitals that exist
in a given shell = n2

66
Quantum Numbers (2)
Angular momentum quantum number,
l

67
Quantum Numbers
Angular momentum quantum
number, l
 Values of l = n-1, 0

68
Quantum Numbers

Angular momentum quantum

number, l
 Values of l = n-1, 0

 Describes the orbital shape

69
Quantum Numbers
Angular momentum quantum
number, l
 Values of l = n-1, 0

 Describes the orbital shape

 Indicates the number of sublevel

(subshells)
(except for the 1st main energy level, orbitals of
different shapes are known as sublevels or
subshells)

* Shape of the “volume” of space that

the e- occupies 70
Orbital Shapes
For a specific main energy level, the number of
orbital shapes possible is equal to n.
Values of l = n-1, 0
 Eg. Orbital which n=2, can have one of two shapes
corresponding to l = 0 or l=1
Depending on its value of l, an orbital is
assigned a letter.

71
Orbital Shapes
Angular magnetic quantum number, l

If l = 0, then the orbital is labeled s.

s is spherical.

If l = 1, then the orbital is labeled p.

p is “dumbbell” shape

If l = 2, the orbital is labeled d.

“double dumbbell” or four-leaf clover

If l = 3, then the orbital is labeled f.

72
Orbital
Shapes
Energy Level and Orbitals
n=1, only s orbitals
n=2, s and p orbitals
n=3, s, p, and d orbitals
n=4, s,p,d and f orbitals
Remember: l = n-1

Value of l 0 1 2 3
Type of orbital s p d f

74
Energy Level Transitions
 Atomic Orbitals
Atomic Orbitals are designated by the
principal quantum number followed by
letter of their subshell

 Eg. 1s = s orbital in 1st main energy level

 Eg. 4d = d sublevel in 4th main energy level

76
Quantum Numbers (3)

Magnetic Quantum Number, ml

77
Quantum Numbers

Magnetic Quantum Number, ml

 Values of ml = +l…0…-l

78
Quantum Numbers

Magnetic Quantum Number, ml

 Values of ml = +l…0…-l
 Describes the orientation of the
orbital
 Atomic orbitals can have the same
shape but different orientations

* orientation of the orbital in space

79
Magnetic Quantum
Number
s orbitals are spherical, only one
orientation, so m=0
p orbitals, 3-D orientation, so m=
-1, 0 or 1 (x, y, z)
d orbitals, 5 orientations, m= -2,-1,
0, 1 or 2

80
Magnetic Quantum Number,
ml
Quantum Numbers (4)
Electron Spin Quantum Number,ms

82
Quantum Numbers
Electron Spin Quantum Number,ms
 Values of ms = +1/2 or –1/2
 e- spin in only 1 or 2 directions
 A single orbital can hold a maximum
of 2 e-, which must have opposite
spins

83
 Orbital Shapes
1) s orbitals(l = 0 )

84
 Orbital Shapes
2) p orbitals(l = 1 )

85
 Orbital Shapes
3) d orbitals(l = 2 )

86
orientation of the orbital in space, ml

ml = -1 ml = 0 ml = 1

ml = -2 ml = -1 ml = 0 ml = 1 ml = 2
7.6
Spin quantum number
ms
ms = +½ or -½

ms = +½ ms = -½

7.6